Liquid laundering compositions



Patented Sept. 4, 1952 free 3,052,635 LIQUID LAUNDERIN G COMPOSITIONSHarold Eugene Wixon, .l'ersey City, Nalfi, assignor to Colgate-PalmoliveCompany, New York, N.Y., a corporation of Delaware No Drawing. FiledDec. 14, 1960, er. No. 75,667 5 Claims. (Cl. 252-137) The presentinvention relates to a detergent composition in the form of a pourable,substantially homogeneous liquid which is suitable for all-purpose useand is particularly effective for laundering purposes, as hereinafterdescribed and claimed.

In the detergent art, it has been common practice to prepare detergentcompositions in powdered form, as obtained by spray-drying a slurry ofthe detergent composition for example. In these powdered products,alkaline builder salts such as sodium tripoly-phosphate andpyrophosphate have been incorporated in significant amounts to improvethe detergency or washing power for the laundering of soiled textilematerials. Other salts such as sodium silicate, carbonate,carboxymethylcellulose and the like have been employed also in thepreparation of pow dered heavy-duty detergent compositions.

In accordance with the present invention, there are prepared heavy-dutyliquid detergent compositions which consist essentially of awater-soluble anionic organic sulfate detergent having an alkyl group ofabout 8 to 18 carbon atoms, a potassium polyphosphate selected from thegroup consisting of pyrophosphate and tripolyphosphate, a higher fattyacid alkylolamide having 2 to 3 carbons in the alkylol radical, analkali metal salt of a lower alkyl aryl sulfonated hydrotropic salt, andan aqueous medium containing a saturated aliphatic monohydric alcoholhaving 2 to 3 carbon atoms, said ingredients being proportioned withinthe ranges described hereinafter to form a pourable, substantiallyhomogeneous product having a total solids content of less than 75% byweight of the composition.

Advantageous embodiments of the invention consist essentially of 5l5parts of said sulfate detergent, -45 parts of said potassiumpolyphosphate, 215 parts of said alkylolamide, 4-12 parts of said arylsulfonate, 4-10 parts of the alcohol and 15-46 parts of water, saidingredients totalling 100 parts and there being less than 75 totalsolids in the liquid composition. A preferred embodiment also containsabout A to 5 parts by weight of sodium carboxymethylcellulose in saidliquid. Various other significant features will be apparent in thefollowing description.

The term pourable as used herein refers to the ability of the product toflow as a liquid from a container at normal room temperatures (e.g.,about C. to C.). The liquid product may be of variable viscosity. It maybe highly fluid and free-flowing, or fairly viscous when at rest butpourable freely from the container upon light shaking. The liquid may bepackaged in any suitable container, however, such as metal, glass orplastic in the form of bottles, cans, drums, packets or bags. The termhomogeneous as used herein means that the product has a satisfactorydegree of stability during storage life against separation or formationof a plurality of distinct layers which either cannot be re-dispersed bylight shaking or which separate rapidly after shaking. Such compositionsinclude liquids which are clear, translucent or opaque depending uponthe type and proportions of the various solids present therein. Anysolid material present in the composition in excess of its solubility inthe particular system is maintained in a non-caking suspension. It ischaracteristic that in such cases, upon light shaking, the product isreadily converted to a substantially homogeneous liquid which is stablefor a sufficient period of time, e.g., at least about 1 hour, so thateach small portion added to a laundering bath or the like will havepractically the same composition. The product exhibits a washing powerwhich is comparable to the same quantity of commercial heavy-dutydetergents in powdered form.

The water-soluble anionic organic sulfate detergents having about 8 to18 carbon atoms in the alkyl group, preferably 8 to 15 carbons, whichare preferred are the aliphatic detergents such as the normal andsecondary higher alkyl sulfate detergents having about 8 to 15 carbonsin the fatty alcohol residue, e.g., lauryl or coconut fatty alcoholsulfate. Alkyl sulfates such as cetyl sulfate and tallow fatty alcoholsulfate may be employed also. Other suitable detergents having such analkyl group of 8 to 18 carbons are the sulfuric acid esters ofpolyhydric alcohols incompletely esterified with higher fatty acids,e.g., lauric, myristic and coconut oil monoglyceride monosulfate,hydrogenated coconut oil monoglyceride monosulfate, and tallow fattyacid monoglyceride monosulfate; higher fatty acid alkylolamide sulfates,e.g., coconut monoethanolamide sulfate, and the like. The sulfateddetergents having said alkyl group and containing a plurality of loweralkylene oxide groups, e.g., within the range of 2 to 20 moles, may beemployed also with suitable adjustment of the proportions in the liquid.Examples are the sulfated fatty alcohols of 8 to 18 carbons condensedwith about 2 to 20 moles of ethylene oxide, e.g., sulfatedlauryl-myristyl alcohols or tallow alcohols condensed with an average of3, 5 and 8 moles ethylene oxide; and the sulfated higher alkylphenol-ethylene oxide condensates having an average of about 2 to 20moles of ethylene oxide per phenol group, e.g., sulfated alkyl phenolhaving 8 to 10 carbons in the alkyl group and an average of 4, 5, 6 and8 moles of ethylene oxide.

These sulfate detergents are used in the form of their water-solublesalts such as the alkali metal and nitrogencontaining, e.g., loweralkylolamine, salts. Examples are the sodium, potassium, ammonium,isopropanolamine, monoand triethanolarnine salts. In commercialpractice, it is preferred to use the alkali metal salts.

The potassium polyphosphate salts have the property of inhibitingprecipitation of calcium and magnesium material in aqueous solution andof contributing to the heavy-duty performance of the liquid detergentproduct in washing operations. While they may be considered as derivedfrom orthophosphoric acid or the like by the removal of molecularlybound water, any suitable means of manufacture may be employed. Suchcomplex or molecularly dehydrated salts may be used in the form of thenormal or completely neutralized salt such as pentapotassiurntripolyphosphate or the partially neutralized salt such as the potassiumacid tripolyphosphate. It is preferred to employ pentapotassiumtripolyphosphate and particularly tetrapotassium pyrophosphate,including any desired combination thereof.

The organic detergent and polyphosphate salts are employ-ed insubstantial amounts such that the addition of a small portion of theliquid product to a washing bath will result in effective washing power.The proportions of these two ingredients are variable and should besuitably selected and proportioned so as to form a pourable,substantially homogeneous product in combination with the otheringredients. In general, proportions within the range from about 0.1 to1 part detergent to 1 part of polyphosphate have been foundsatisfactory, and preferably about 0.2 to 1 part deter-gent for eachpart of polyphosphate where said detergent and polyphosphate total atleast about 20% by weight. The amount of detergent will be usually aboutto 15% by weight and the amount of potassium polyphosphate will be about15 to 45%, preferably 15 to 30%, by weight of the composition asformulated. As a general guiding principle, it is advisable to vary thedetergent and polyphosphate contents conversely, i.e., relatively lowamounts of one are used when relatively high amounts of the other aredesired in the product.

The water-soluble hydrotropic sub-stance which has been found to beparticularly effective in the liquid detergent composition is an alkalimetal lower alkyl aryl sulfonate salt, preferably the sodium andpotassium toluene and xylene sulfonate salts. Sulfonates made fromxylene include orthoxylene sulfonate, metaxylene sulfonate, paraxylenesulfonate and ethylbenzene sulfonate. Commercial xylene sulfonatesusually contain metaxylene sultfonate as the main ingredient. Analysesof typical commercial products shown about 40-50% metaxylene sulfonate,35% orthoxylene sulfonate and -30% paraxylene sulfonate with 020%ethylbenzene sulfonate. Any suitable isomeric mixture may be employed,however. The hydrotropic material promotes the compatibility of theingredients and assists in forming a homogeneous product. The hydrotropemay be employed in variable amounts depending upon the proportions ofthe other ingredients, but ordinarily it will be present in a suitableamount from about 4 to about 12%, preferably about 4 to 10%, by weightof the composition.

The higher fatty acid alkylolamide functions in a suitable amount as asuds builder during washing operations and provides a solubilizingeffect in certain formulations to aid in the stability of the product.In general, the alkylolamide may be employed in an amount from about 2to 15% by weight in the product, and preferably from about 3 to 8%. Theacyl radical of the alkylolamide is selected from the class of fattyacids having 8 to 18 carbons and each alkylol group has up to 3 carbonatoms usually. It is preferred to use the diethanolamides,isopropanolamides and monoethanolamides of fatty acids having about 10to 14 carbons in the acyl radical. Examples are the lauric, capric,myristic and coconut diethanolamides, monoethanolamides amides, andmixtures thereof. There may be employed also the alkylolamides which aresubstituted by additiona1 alkylol groups, suitable examples being theabove monoethanolamides, diethanolamides and isopropanolamides condensedwith one or two moles of ethylene oxide.

The aqueous medium should contain a saturated aliphatic monohydricalcohol of 2 to 3 carbon atoms such as ethanol, propanol, orisopropanol. Depending upon the proportions of the other ingredients ina particular composition, the alcohol may serve a multiplicity offunctions. In general, the alcohol is used in variable amounts so as toimprove the physical properties. The alcohol may be employed in anamount from about /2 to and preferably from about 4 to 10% alcohol. Thealcohol serves as a solubilizing ingredient also and the resultingcompositions may be clear or opaque depending upon the proportionsemployed. The alcohol may function to prevent unduly rapid separation orformation of non redispersible phases in the liquid.

In addition, the alcohol permits desired modification of the viscosity,such as to make the product less viscous where high solids are employedand improve pourability and isopropanol- 4 thereby. It can provide forimproved low temperature aging of the product such as the prevention ofa precipitate at moderately low temperatures, e.g., about 40 F., whichdoes not redisperse upon recovery to room temperature. The alcohol mayadjust also the phase relationship so as to lower the cloud point andinsure a clear liquid at a lower temperature if desired. In general, ittends also to minimize foaming and aeration of the product dur ingmanufacture and upon shaking of the container so as to permit pouring ofuniform portions thereof. These improvements may be effected usuallywith relatively small amounts of alcohol, e.g., up to about 10% byweight. There is a critical maximum proportion of alcohol since anexcessive amount will result in separation of the product into two ormore layers which either separate rapidly or will not redispersereadily. The amount of alcohol used should not adversely affect thehomogeneity of the liquid therefore, such as by separation of inorganicsalt solution or by excessively thinning a high solids product whererelatively high viscosity is desired as an aid in preventing rapidseparation.

The presence of the combination of the solubilizing agents permitsincreased flexibility for variation in formulation so as to obtain arange of physical properties which is not possible by the use of theseingredients individually. In liquid systems containing relatively lowamounts of detergent and phosphate or medium amounts of detergent andrelatively low phosphate within the ranges claimed, it is possible toobtain clear liquids at room temperature by use of suitable proportions.In systems containing medium to high amounts of detergent and phosphatewithin the ranges described, there is produced a lotion-like or opaqueliquid. There may be obtained homogeneous liquids with this combinationusing amounts of the alcohol and the hydrotropic salt for example whichindividually do not provide a product of sufficient homogeneity orpourability. For example, where the solids concentration is at a highlevel, the amount of hydrotropic salt which may be added is limitedsince it will increase the solids content. Where the solids content isexcessive, a nonpourable product will be obtained. The presence of thealcohol in combination will permit the formulation of the desired liquidproduct.

In general, the solids content should be less than about 75% and usuallyup to about 65% by weight in the composition. It is preferred to have amaximum of about 60% solids for opaque liquids and up to about 50%solids for clear solutions. The balance of the liquid content isprimarily water since the liquid alcohol is used in small amounts. Theamount of water will be suitably proportioned to provide suflicientsolubilizing effects for the phosphates and similar organic salts so asto form a substantially homogeneous product. The amount of water isvariable depending upon the solids content and the proportion ofalcohol. The water is generally up to about 60% by weight of thecomposition. In liquids of solids content above about 50% by weight, itis preferred to employ about 4 to 20% of alcohol and a suitable :amountof water from the range of 15 to 46% by weight. In liquids of solidscontent up to about 50%, it is preferred that the amount of water be atleast about 30% by weight.

The inclusion of a suitable soil anti-redeposition agent is consideredparticularly desirable for highly effective laundering purposes. Suchmaterials are bydrophilic colloids and are maintained in dispersedcondition in the product. It has been found possible to retain thecellulosic ethers in the concentrated system, particularly alkali metal,e.g., sodium and potassium, carboxymethylcellulose. It is preferred touse sodium carboxymethylcellulose for optimum effects. Other suitablewatersoluble cellulosic or starch derivatives may be employed in thecomposition such as the lower alkyl and hydroxyalkyl ethers, e.g.,methyl-, ethyl-, and hydroxyethylcellulose. It has been found thatwater-soluble (colloidally soluble) polymers such as polyvinyl alcoholand polyvinylpyrrolidone are compatible in the system also. Thecellulosic material or the like should be employed in minor proportion,such as about A to 5% by weight, though lesser amounts such as 0.1% maybe employed.

The liquid detergent product is prepared in any suitable manner. Thehydrotropic salts, the polyphosphate and the organic detergent are addedin the form of powders, aqueous solutions or slurries to the aqueousmedium as desired. The alkylolamide is preferably added in molten orliquid form with agitation to form a homogeneous mixture. The alcoholmay be added at any stage during the mixing operations as desired. Thetemperature of admixture is not critical and room temperatures orreasonable elevated temperatures may be employed.

The following examples are illustrative of the nature of the inventionand it will be understood that the invention is not limited thereto. Allamounts are in approximate weight percent.

Example I Ingredient: Percent Sodium lauryl sulfate 9.61 Potassiumtripolyphosphate 24.00 Potassium toluene sulfonate 6.40 Coconutdiethanolamide 8.00 Sodium carboxymethylcellulose 1.44 Ethanol 15.60

Water (Q.S. to 100%). The above product is an opaque, pourable liquidwhich separates upon aging but is redispersed upon light shaking to ahomogeneous form of suflicient stability.

Example II Ingredient: Percent Sodium lauryl sulfate 15 Potassiumpyrophosphate 15 Sodium xylene sulfonate 6 Potassium toluene sulfonate 2Coconut diethanolamide 6 Ethanol 5 Water (Q.S. to 100%).

The above product is an opaque, poura-ble homogeneous liquid at roomtemperature which has a cloud point of 77 F. and a clear point of 86 F.An increase in the alcohol content to 7 /2% provides for a more fluidlotion-like product. In the absence of the alcohol, there is obtained anon-pourable solid at room temperature.

Example III Ingredient: Percent Sodium hydrogenated coconut fatty acidmonoglyceride monosulfate 15 Potassium pyrophosphate 30 Sodium xylenesulfonate 8 Coconut diethanolamide 10 Ethanol 8 Water (Q.S. to 100%).

Example IV Ingredient: Percent Sodium hydrogenated coconut fatty acidmonoglyceride monosulfate 5 Potassium pyrophosphate 40 Water (Q.S. to100%).

The products of Examples III and IV are opaque, lotion-like homogeneousliquids and the product of Example V is a clear solution at roomtemperature.

Examples VI-VII vr, percent VII,

Ingredient percent Sodium suliated nonyl phenol condensed with 5 molesof ethylene oxide Sodium xylene sulfonate Coconut diethanolamide EthanolWater (Q.S. to

The products of Example VIVII are clear solutions. Examples VIII-IXVIII, percent Ingredient percent [Orwwoooo The product of Example VIIIis a clear solution and the product of Example IX is an opaque,homogeneous liquid.

Various other ingredients may be added or substituted if desired. In aliquid containing a plurality of components, the individual solubilitycharacteristics of added materials may influence the physical propertiesof the liquid. It is understood therefore that such ingredients will besuitably selected and the proportions of the various componentscontrolled as described herein so: as to form a liquid product havingthe desired physical qualities. Thus, there may be included suitableamounts of various anionic sulfonate or nonionic organic detergents.Other adjuvant materials include compatible perfumes, coloring material,corrosion inhibitors, antitarnishing agents, germicides, bleachingagents, optical bleaches or fluorescent dyes, and the like. If desired,there may be included other phosphate materials or similar builder saltssuch as silicates in the product provided that they do not substantiallyadversely affect the product.

This application is a continuation-in-part of my prior applicationSerial No. 532,735, filed September 6, 1955, now abandoned.

Although the present invention has been described and illustrated withreference to specific examples, it is understood that modifications andvariations of composition are contemplated within the scope of theappended claims.

What is claimed is:

1. A liquid detergent composition consisting essentially of about 5 to15 parts by weight of a water-soluble anionic organic sulfate detergenthaving an alkyl group of about 8 to 18 carbon atoms, about 15 to 45parts by weight of a potassum polyphosphate selected from the groupconsisting of pyrophospha-te and tripolyphosphate, about 2 to 15 partsby Weight of a higher fatty acid alkylolamide having 8 to 18 carbonatoms in the fatty acid radical and 2 to 3 carbon atoms in the al-kylolradical, about 4 to 12 parts by weight of an alkali metal salt of alower alkyl substituted benzene hydrotropic sulfonated salt having up totwo carbon atoms in said alkyl substituent, and an aqueous alcoholicmedium having about /2 to 20 parts by weight of a saturated aliphaticmonohydric alcohol having 2 to: 3 carbon atoms, said ingredients beingproportioned to form a pourable, substantially homogeneous producthaving less than 75% total solids by weight in the liquid detergentcomposition.

2. A liquid detergent composition consisting essentially of about 5 to15 parts by Weight of a water-so-luble anionic organic sulfate detergenthaving an alkyl group of about 8 to 15 carbon atoms, about 15 to 45parts by Weight of a potassium polyphosphate selected from the groupconsisting of pyrophosphate and tripolyphosphate, about 2 to 15 parts byWeight of a fatty acid alkylolamide having about 10 to 14 carbon atomsin the fatty acid radical and 2 to 3 carbon atoms in the alkylolradical, about 4 to 12 parts by Weight of an alkali metal salt of loweralkyl benzene sulfonic acid selected from the group consisting of sodiumand potassium Xylene and toluene sulfonates, about /2 to 20 parts byweight of a saturated aliphatic monohydric alcohol having 2 to 3 carbonatoms, and the balance being primarily water, said ingredients beingproportioned to form a pourable, substantially homogeneous product andthe amout of total solids being less than 75% by weight in said liquiddetergent composition.

3. A liquid detergent composition consisting essentially of thefollowing ingredients proportioned within the stated ranges in parts byWeight to form a pourable, substantially homogeneous product: about 5-15parts of a water-soluble anionic organic sulfate detergent having analkyl group of about 8 to 15 carbon atoms, about 15-45 parts of apotassium polyphosphate selected from the group consisting ofpyrophosphate and tripolyphosphate, about 2-15 parts of a fatty acidalkylolarnide having about 10 to 14 carbon atoms in the fatty acidradical and 2 to 3 carbon atoms in the alkylol radical, about 4-12 partsof an alkali metal salt of a lower alkyl benzene sulfonic acid selectedfrom the group consisting of sodium and potassium xylene and toluenesulfonates, about 4-10 parts of an alcohol selected from the groupconsisting of saturated aliphatic monohydric alcohols having 2 to 3carbon atoms, and 15-46 parts water, there being less than 75 totalsolids in the liquid detergent composition.

4. A liquid detergent composition as set forth in claim 3 which alsocontains about A to 5 parts by Weight of sodium carboxymethylcellulose.

5. A liquid detergent composition consisting essentially of thefollowing ingredients proportioned within the stated ranges in parts byWeight to form a pourable, substantially homogeneous product: about 5-15parts of an alkali metal anionic organic sulfate detergent having analkyl group of about 8 to 15 carbon atoms, about 15-30 parts of apotassium polyphosphate selected from the group consisting ofpyrophosphate and tripolyphosphate, about 2-15 parts of a fatty acidalkylolamide having 10 to 14 carbon atoms in the fatty acid radical andselected from the group consisting of diethanolamides,monoethanolamides, and isopropanolarnides, about 4-12 parts of an alkalimetal salt of a lower alkyl benzene sulfonic acid selected from thegroup consisting of sodium and potassium Xylene and toluene sulfonates,about 4-10 parts of ethanol, and the balance being primarily Water,there being less than 75% total solids in the liquid detergentcomposition.

References Cited in the file of this patent UNITED STATES PATENTS2,581,677 Machlis Jan. 3, 1952 2,607,740 Vitale Aug. 19, 1952 2,877,187Henderson Mar. 10, 1959 OTHER REFERENCES Trexler: Soap and SanitaryChemicals, July 1950, pp. 39-41, 82.

1. A LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 5 TO15 PARTS BY WEIGHT OF A WATER-SOLUBLE ANIONIC ORGANIC SULFATE DETERGENTHAVING AN ALKYL GROUP OF ABOUT 8 TO 18 CARBON ATOMS, ABOUT 15 TO 45PARTS BY WEIGHT OF A POTASSIUM POLYPHOSPHATE SELECTED FROM THE GROUPCONSISTING OF PYROPHOSPHATE AND TRIPOLYPHOSPHATE, ABOUT 2 TO 15 PARTS BYWEIGHT OF A HIGHER FATTY ACID ALKYLOLAMIDE HAVING 8 TO 18 CARBON ATOMSIN THE FATTY ACID RADICAL AND 2 TO 3 CARBON ATOMS IN THE ALKYLOLRADICAL, ABOUT 4 TO 12 PARTS BY WEIGHT OF AN ALKALI METAL SALT OF ALOWER ALKYL SUBSTITUTED BENZENE HYDROTROPIC SULFONATED SALT HAVING UP TOTWO CARBON ATOMS IN SAID ALKYL SUBSTITUENT, AND AN AQUEOUS ALCOHOLICMEDIUM HAVING ABOUT 1/2 TO 20 PARTS BY WEIGHT OF A SATURATED ALIPHATICMONOHYDRIC ALCOHOL HAVING 2 TO 3 CARBON ATOMS, SAID INGREDIENTS BEINGPROPORTIONED TO FORM A POURABLE, SUBSTANTIALLY HOMOGENEOUS PRODUCTHAVING LESS THAN 75% TOTAL SOLIDS BY WEIGHT IN THE LIQUID DETERGENTCOMPOSITION.